Diamino tricyclodecane



United States l atent 3,069,468 DIAMINO TRICYCLUDECANE Eugene F. Cox, South Charleston, David T. Manning, Charleston, and Harry A. Stansbury, in, South Charleston, W. Va., assignors to Union Carbide Corporation, a corporation of New York N0 Drawing; Filed Mar. 16, 1959, Ser. No. 799,409 1 Claim. (Cl. 260-563) This invention relates to certain novel tricyclodecanes and to a process for their preparation. More particu- 1 larly, the present invention relates to 3,10-diaminotricyclo[5.2.1.0 ]decane and its functional derivative, 3,10- diisocyanatotricyclo [*5.2.1.0 ]decane.

The novel materials of the present invention may be a brihs t ri s aeri l ema wherein R is selected consisting of NH and N.:C=O. 'ij s I .The novel 3,lO-diaminotricyclo[5.2.1.0 ]decane of the present invention can be condensed with dibasic acids xto form valuable and useful polyamide resins.

(1) 2C H OH 2Na ethanol sodium (2) C H ONa NOCl sodium nitrosyl ethoxide chloride cyclopentadiene ethyl nitrite carbon dioxide 3,969,468 Patented Dec. 18, 1962 ice genation is a known compound which can be prepared from cyclopentadiene, nitrosyl chloride, and sodium ethoxide by the methods described in copending application Serial No. 783,701. The hydrogenation reaction should be conducted in the presence of from 1 to 250 mols, per mol of dioxime, of anhydrous ammonia and preferably is conducted using from about 5 to about mols of anhydrous ammonia per mol of dioxime. The hydrogenation may be conducted at a temperature of from about 0 to about 250 C. but is preferably conducted at a temperature of from about 25 to about 200 C. and at a pressure of from about to 4000 p.s.i.g., preferably from about 1000 to about 2000 p.s.i.g. A hydrogenation catalyst should preferably be employed. Suitable hydrogenation catalysts include Raney nickel, cobalt, platinum, palladium, and the like. The catalyst should be present in an amount corresponding to from about 5 to about 100 weight per mol of dioxirne. While not essential to the reaction, an inert solvent, such as methanol, p:dio Xane, ethanol, or diethylene glycol diethyl ether may be employed in an amount corresponding to from about 2 to about 50 parts by weight per part of dioxime.

3,lO-diisocyanatotricyclo[5.2.1.0 ]decane can be prepared by reacting 3,lO-diaminotricyclo[5.2.1.0 ]decane with phosgene. The phosgene should be employed in an amount corresponding to from about 2 to 200 mols per mol of the decane. The reaction should be conducted at a temperature of from about 50 to about 350 C., preferably from about 100 to about 300 C. and should be conducted in the presence of inert solvents such as benzene, toluene, chlorobenzene, dichlorobenzene, trichloroben- Zene, chlorinated toluene, chlorinated xylenes, chlorinated naphthalenes, sulfolanes, and tetrahydronaphthalene.

The following example is illustrative of the preparation of the dioximino compound employed in the present invention:

EXAMPLE I m EGHONa-i-H sodium ethoxide C H ONO NaCl ethyl sodium nitrite chloride 2C H OH sodium NONa ethanol ethoxide sodium salt of oximinocyclopentadiene IEOH NOH -...,.---- 2NaHCO sodium. bicar-- bonate spegaee Anhydrous ethanol (3000 ml.) was stirred and refluxed, while 69 grams of sodium metal (3 moles) were dissolved. The resulting solution of sodium ethoxide was stirred at to C. while 94 grams of nitrosyl chloride (72 ml. at 30 C., 1.56 moles) were fed over a period of minutes. The mixture was stirred at 2 to 7 C. While 94.5 grams of freshly distilled cyclopentadiene (1.43 moles) were fed over a period of 2 hours. After a reaction period of 2 hours at 7 to 22 C., the reaction mixture was added to 1500 ml. of cold water (5 C.) and stripped to a kettle temperature of 25 C. at 10 mm. to remove ethanol. The residue was extracted several times with ethyl ether to remove base-insoluble impurities. The basic aqueous solution (pH 12) was saturated with carbon dioxide at 8 C. to reduce the pH to 7.8 and precipitate the crude dioxime. Both the pre- 'cipitate and the aqueous layer were extracted continuously with ethyl ether to separate the dioxime from tarry by-products. Evaporation of the ether from the extract yielded 87.5 grams (64 percent yield) of dioxime as a light tan solid in several crops melting in the range of 155 to 162 C. An analytical sample was prepared by dissolving 20 grams of the dioxime in 100 ml. of 2 N sodium hydroxide plus ml. 'of water. After filtration, the solution was neutralized with carbon dioxide and extracted with ethyl ether several times. The extracts were combined and the ether evaporated to obtain 17.2 grams of pure dioxime of melting point 160 to 164 C. Found 63.0 percent C (theory 63.14 percent), 5.9 percent H (theory 5.3 percent), 14.3 percent N (theory 14.7 percent). The infrared absorption spectrum supported the 1,8-dioximino-4,7- m ethano-3a,4,7,7atetrahydroindene A mixture of 64.3 grams (0.338 mole) of 1,8-dioxi-mino 4,7 methano 3a,4,7,7a tetrahydroindene, 250 grams of Raney nickelcatalyst, and 1500 ml. of ethanol was divided equally between two 3-liter stainless steel rocker autoclaves. 689 grams of anhydrous ammonia (40.5 moles). Thus the molar ratio of ammonia to dioxime was 240/ 1. Each charge was then hydrogenated at 1000 to 1600 p.s.i.g. to a maximum temperature of 90 C. The hydrogen absorption appeared to be complete after two hours at 27 C., but the temperature was gradually increased to C. over a period of six hours to ensure complete hydrogenation. The hydrogenated mixtures were combined, filtered to remove catalyst, and distilled to isolate 4.1 grams of To each autoclave was then added 50 A. with perchloric acid. Since the theoretical equivalent weight for the diamine is 83, the purity was 98.6 percent. The yield was 72 percent based on the dioxime. The distillation residue Weighed only 4.8 grams and the ratio of distilled product to residue was 8.5.

EXAMPLE III TABLE I Equivalent; Fraction Weight Distillation range weight as grams amine 5. 8 96100 C./1 mm 96. 5 8.0 110-125" C./2 mm 101.0 27. 2 126. 7

The residue had a molecular weight of 351 by the Menzies-Wright method. The yield of 3,10-diaminotricyclo[5.2.1.0 ]decane in this experiment was about 16 percent based on the dioxime.

3,10-diaminotricyclo [5.2.1.0 decane heating gradually to 100 C. over a period of 5 hours. The filtered mixture was distilled to obtain the fractions listed below in Table II.

TABLE H Weight, Equivalent Fraction grams Distillation range weight as amine 1 15; 7 8398 (ll/.5 111111 86. 8 7.4 98-130" O./.5 mm 93. 4 Residue 18. 0 121. 8

The yield of 3,l0-diaminotricyclo[5.2.1.0 ]decane was about 43 percent based on the dioxime.

EXAMPLE V H NH H NCO H NH NCO 3,lO-diaminot iphosgene 3 lo-diisocyanat', hydrogen cyclogfiifl t;-j y 1o[5".2.l.( chloride ecane decane 3,10-diaminotricyclo[5.2.1.O ]decane as a colorless liquid having these properties: boiling range 87 to 98 C./0.5.mm., 84.2 equivalent weight as amine by titration A solution of 3,1O-diaminotricyclo[5.2.1.0 ]decane (33-3 grams, 0-20 mole) in 300 ml. of o-dichlorobenzene was st rred at 90 to 0. while carbon dioxide was bubbled in for 22 hours. The resulting slurry was cooled to -5" C., and 90 grams of phosgene were added dropwise with stirring during one hour. More phosgene (36 grams) was added while the slurry was allowed to warm to room temperature. The slurry was heated to 160 C. and phosgene addition continued at an approximate rate of 25 grams per hour for ten hours. After purging with nitrogen and removal of solvent under reduced pressure, 39 grams of 3,1O-diisocyanatotricyclo[5.2.1.0 ]decane were distilled, boiling point 130 to 134 C./ .5 mm. The yield was 90 percent based on the diamine.

Analysis.-Calculated for C H N O C, 66.02; H, 6.47; N, 12.84. Found: C, 66.10; H, 6.67; N, 12.48.

EXAMPLE VI Polyurethane Foam Prepared From 3,10-Diis0- cyarzat0tricycl0[5 .2 .1 .0 ]Decane Ten grams of a polyester of adipic acid and diethylene glycol, 4.4 grams of 3,l0-diisocyanatotricyclo- [5.2.1.0 ]decane, and 0.3 gram of emulsifier comprising a nonionic fatty arnido condensate were thoroughly mixed in a beaker. Dibutyltin acetate catalyst (0.15 gram) was added and mixing continued until the temperature of the mixture rose to 35 C. Water (0.20 gram) was then added and rapidly stirred into the mixture. Foaming occurred after a four-minute exposure in an oven at C. Unless otherwise indicated, as used throughout this specification, all parts and percentages are by weight.

What is claimed is: 3,1O-diaminotricyclo[5.2.1.0 decane.

References Cited in the file of this patent UNITED STATES PATENTS 2,822,373 Beck Feb. 4, 1958 2,850,532 Simon et al Sept. 2, 1958 2,864,863 Young Dec. 16, 1958 2,875,226 Bloom et al. Feb. 24, 1959 OTHER REFERENCES Prelog et al.: Ber. Deut. Chem., vol. 74, pages 1769- 1772 (1941).

Elsevier: Elseviers Encyclopedia of Organic Chemis try, vol. 12A, page (1948).

Reppe et al.: Ann. der. Chemie, vol. 560, pages 1-92 (1948).

Wilder et al.: J.A.C.S., vol. 81, pages 655-658 (1959).

(Copies of above in Patent Office Sci. Lib.) 

